CN101835707A - A filter material for generating oxygen and/or hydrogen from a source - Google Patents
A filter material for generating oxygen and/or hydrogen from a source Download PDFInfo
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- CN101835707A CN101835707A CN200880113156A CN200880113156A CN101835707A CN 101835707 A CN101835707 A CN 101835707A CN 200880113156 A CN200880113156 A CN 200880113156A CN 200880113156 A CN200880113156 A CN 200880113156A CN 101835707 A CN101835707 A CN 101835707A
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- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
- C01B3/042—Decomposition of water
- C01B3/045—Decomposition of water in gaseous phase
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- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
- C01B13/02—Preparation of oxygen
- C01B13/0203—Preparation of oxygen from inorganic compounds
- C01B13/0207—Water
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- C01—INORGANIC CHEMISTRY
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- C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
- C01B13/02—Preparation of oxygen
- C01B13/0229—Purification or separation processes
- C01B13/0248—Physical processing only
- C01B13/0259—Physical processing only by adsorption on solids
- C01B13/0262—Physical processing only by adsorption on solids characterised by the adsorbent
- C01B13/027—Zeolites
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- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
- C01B3/042—Decomposition of water
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- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
- C01B3/501—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by diffusion
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- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62B—DEVICES, APPARATUS OR METHODS FOR LIFE-SAVING
- A62B19/00—Cartridges with absorbing substances for respiratory apparatus
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- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62B—DEVICES, APPARATUS OR METHODS FOR LIFE-SAVING
- A62B21/00—Devices for producing oxygen from chemical substances for respiratory apparatus
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- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
- C01B2203/0405—Purification by membrane separation
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- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
- C01B2203/0465—Composition of the impurity
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- C01B2210/00—Purification or separation of specific gases
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- C01B2210/0046—Nitrogen
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- C01B2210/00—Purification or separation of specific gases
- C01B2210/0043—Impurity removed
- C01B2210/0053—Hydrogen
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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Abstract
A filter material for generating oxygen and/or hydrogen gas from a source having a porous boron doped carbon film with diRuthenium/diRuthenium molecules in direct contact with the porous boron doped carbon film, a synthetic film having at least one zeolite crystalline body in direct contact with the nanocarbon tubules, or both in a continuous alternating arrangement.
Description
The cross reference of related application
The application requires the right of priority of the U.S. Provisional Application 60/967,756 of submission on September 7th, 2007, and described application is merged in this paper as a reference.
Invention field
The atmospheric oxidation that the present invention relates to water and/or exhalation is the filtering material of bimolecular oxygen and/or hydrogen gas.Especially, relate to and comprise at least a two rutheniums/two ruthenium complexs of being fixed in boron doping type carbon film and comprise the film forming filtering material of closing of crystallization of zeolites.Filtering material of the present invention has been not only owing to having used two rutheniums/two ruthenium complexs that high separation efficiency is provided, and combines with the high fractionation by adsorption efficient that embeds the zeolite that CNT (carbon nano-tube) is arranged by the catalyst property with two rutheniums/two ruthenium complexs other separation efficiency is provided.
Background of invention
In history, electrolysis, photolysis and the chemical conversion by water realizes that oxygen generates.Be transformation sorption cycle (" PSA ") still now in a method of using, as United States Patent (USP) 2,944, described in 627, described document is merged in this paper as a reference.In the PSA system, by selecting absorption nitrogen to produce oxygen from raw air stream.PSA has at least one, often is two adsorbent beds that it is designed for and attracts oxygen and discharge adsorbed oxygen at high pressure under low pressure.The PSA method can be used for the gas in the separating mixture, because some gas tends to be attracted by different solid surface more consumingly or less intensely than other gas.
Another utilize the oxygen generation method of some principles of PSA method be called as vacuum change absorption (Vacuum Swing Adsorption, VSA).In " VSA " method, the applying pressure divided gas flow, but different with the PSA method, it is to carry out under lower absolute pressure.Although these methods have effect, they need a plurality of pressurizing vessels and valve system, make to be difficult to carry, even can not carry.That is to say these systems need carry out automatically or valve operation by circulating and carry out by the careful timing of calculating of the process of PLC control.Therefore, these systems are sizable, and hinder the patient that the oxygen generation system is directly worn as portable system thus.
In these years, carried out improvement, such as being merged in this paper United States Patent (USP) 3,313,091 as a reference to PSA and VSA system.Although PSA in the past and VSA system use transforming valve and zeolite adsorption material to come the product of production high oxygen purity, these systems are instability but also remarkable not only.In order to keep stable oxygen product, US 3,313, and 091 uses vacuum pump to extract the adsorbate that a part is called as " waste gas body " out from the container or the bed that are purged.Yet, the more complicated electromechanics design annexation of these progressive needs that is better than former PSA and VSA system, comprise additional control mutually, for example inlet mouth, vacuum are pressurizeed and are removed, with allow with higher yield provide to shift by and pass to user or patient's oxygen as the product of several cycles.So also do not remedy with nitrogen and load: oxygen is than (nitrogen loading tooxygen ratios) or the build-up of electrostatic charges on zeolite surface, obstruction and obstruction transfer and silt relevant problem up.
The next one progress of oxygen filtration aspect appears at 1980, and is described in United States Patent (USP) 4,222, and in 750, described patent is merged in this paper as a reference.In this patent, the container of absorption filtering material or bed experience wherein said container or bench grafting circularly to be subjected to use vacuum pump from resorbent two cycles of bed then from the absorption of the gas of compressor.As seen, more equipment has been added by this system of being improved to, and makes it more impossible as portable system.
Therefore, need to be used to generate in the portable respiration device strainer of the oxygen of sufficient quantity, it can not have build-up of electrostatic charges, nitrogen to load: oxygen absorption is used than under, the situation about stopping up, and gets rid of expensive and bulky pumping chamber/valve and other big equipment.Need and to produce the filtering material of oxygen to keep needed speed of patient respiratory and concentration, and need not the valve system of pressurized compartment and underpressure chamber and opening and closing complexity.The invention provides the shortcoming that overcomes prior art and can be used for the filtering material of portable oxygen generation system veritably, described oxygen generation system can be kept the required suitable oxygen level of patient respiratory.In with the lower section, the present invention is discussed.
Summary of the invention
The present invention relates to the filtering material that do not need the pumping chamber to operate.Especially, the present invention relates to comprise the filtering material that is used for removing oxygen and/or hydrogen gas of porous boron doping type carbon film from the air of water and/or exhalation, comprise the two rutheniums/two ruthenium molecules and at least a electronegative ion that directly contact with porous boron doping type carbon film, generate oxygen and/or hydrogen from described source when crossing described filtering material in the source thus.
In one embodiment of the invention, one two ruthenium molecule in each two ruthenium of boron doping type carbon film/two ruthenium molecules is formula [Ru
2(CO)
4(u-n
2-O
2CR)
2L
2]
x, wherein u is selected from following bridgingligand: [Ru
2(EDTA)
2]
2-, (CO)
4, F
-, Co
3 -2, NO
+Aromatic series/the carboxylic acid of (cationic), hydrogen bonding-(being used for multiple connection such as polymerization or one), quadrol, halogen ion, carboxylic acid, unsaturated hydrocarbons, linear or crooked and metal center coordinate nitric acid, divinyl, carboxylicesters part, anionic (RO as the anionic part at the oxygen or the interior location of two bondings
-And RCO
2 -2(wherein R is H or alkyl) or neutral ligand (R
2, R
2S, CO, CN
-), CH
3CN (acetonitrile), NH
3(ammonia ammine) F
-, Cl
-, three (pyrazolyl) borate (scorpion is closed part, Scorpionate Ligand, a boron combines with three pyrazoles, this compound-two pyrazole group (C that chela (pincers)-be meant can bond
3H
4N
2) nitrogen heteroatom)) and composition thereof, preferred [Ru
2(EDTA)
2]
2-
Wherein the n minimum is 2, and depends on the number of teeth (denticity) (that is the number of the donor groups that is connected in the identical central atom of given part) of molecule;
Wherein L is selected from following part: [Ru
2(Ph
2PCH
2CH
2PPh
2) (EDTA)]
2+, C
6H
6, R
2C=CR
2(wherein R is H or alkyl), 1, the two diphenyl phosphine methane of 1-, diethylenetriamine [diene] key (preferred three teeth), 7-triazacyclononane [diene] key (preferred three teeth), triphenyl phosphine and composition thereof;
Wherein CR is carboxylic acid, carboxylicesters part, anionic (RO
-And RCO
2 -(wherein R is an alkyl)) or neutral ligand (R
2, R
2S, CO
-, CN
-(wherein R is an alkyl)) and composition thereof; About 30 for about 1-with x, preferably 1-is about 20, and more preferably 1-about 10.
Another two rutheniums molecule in each two ruthenium of boron doping type carbon film/two ruthenium molecules is connected in as formula [WZnRu
III 2(OH) (H
2O) (ZnW
9O
34)
2]
-14The multi-metal oxygen acid group that replaces of two rutheniums of electrochemical catalyst.Except these features, described porous boron doping type carbon film can comprise the CNT (carbon nano-tube) mesh network of embedding in addition.
Because if ruthenium ion discharges from strainer, this ion can have side effects to the patient, catches siderophore so filtering material of the present invention can comprise ruthenium ion in addition.Described siderophore can be connected in the apparent surface of the porous boron doping type carbon film that wherein connects two rutheniums/two ruthenium molecules.Siderophore can be the shape of plate, perhaps can form the structure of the hollow tube of being made by light metal alloy (for example aluminum bronze oxide compound), and described hollow tube is poly-sulfuric ester resin (polysulfate resin), EDTA or its mixture of dipping.Described hollow tube can have a plurality of holes of the dispersive of running through, so that help to catch the charged ion of free ions.Especially, described siderophore can be charged, so that may before the dispossessed any free ruthenium ion of porous boron doping type carbon film enters in patient's body it caught.
Filtering material can also comprise thin synthetic film, has the carbon nanotube that is connected in described film and the crystallization of zeolites body that directly contacts with described CNT (carbon nano-tube).Zeolite is the aluminium silicate mineral matter of hydration typically, has multi-cellular structure.Therefore, the synthetic film of synthetic zeolite of the present invention plays the effect of molecular sieve, and the overall dimension that wherein can enter molecule in the hole of zeolite or ionic species is subjected to the control of the channel diameter that is limited by the ring size in hole usually in the molecular sieve.For example, the zeolite composition with 8 ring structures is silicon or the aluminium by 8 tetrahedral coordinations) closed circuit of atom and 8 Sauerstoffatom structures and itself constitute many holes.In other words, the size control specific ion in the hole in the zeolite synthesis film enters into this internal void space of zeolite synthesis film, and it is by the number decision of T atom (T=Si or Al) in the ring and oxygen.Hole sort is super large (＞12 yuan rings), big (12), medium (10) or little (8).The size range in hole forms about 0.4nm (8 yuan of ring texturees), such as zeolite A; About 0.54nm (10 yuan of ring texturees) is such as ZSM-5; With about 7.4nm (12 yuan of ring texturees),, above-mentionedly all may be used to the present invention such as X zeolite and ZSM-12.
Synthetic film itself comprises many holes of the about 3.0nm of the about 0.1-of diameter, and oxygen sieve effect (O is provided
2=2.96 dusts, N
2=3.16 dusts).The crystallization of zeolites body that is connected in CNT (carbon nano-tube) covers the hole of at least a portion.Comprise the porous boron doping type carbon film of two rutheniums/two ruthenium molecules and be connected with carbon nanotube and thin synthetic film that crystallization of zeolites body and CNT (carbon nano-tube) directly contact forms repeating unit, can be used for constituting the strainer that can be used for removing oxygen and/or hydrogen from supply source.
Other embodiments of the present invention and details provide in accompanying drawing and detailed Description Of The Invention part.
The accompanying drawing summary
Fig. 1 shows the front prediction view of the porous boron doping type carbon film that comprises two rutheniums/two ruthenium molecules of filtering material of the present invention.
Fig. 2 shows the back side prediction view of the porous boron doping type carbon film that comprises two rutheniums/two ruthenium molecules and siderophore plate of filtering material of the present invention.
What Fig. 3 showed filtering material of the present invention comprises the film forming surperficial sectional view of closing of crystallization of zeolites body.
Fig. 4 shows a plurality of alternately sectional views of screen (screen) of filtering material of the present invention.
Fig. 5 shows a plurality of alternately prediction views of screen of the filtering material of the present invention in cartridge filter.
Detailed Description Of The Invention
The present invention relates to generate the filtering material of many oxygen, comprise alternately two kinds of different catalyst screens of orientation. Two rutheniums/two rutheniums screen plays the effect of the eelctro-catalyst that generates oxygen, and another is zeolite, is the absorption screen. Embedding has described two kinds of screens of CNT mesh network all to allow together or respectively to produce more oxygen and realize much higher flow rate than prior art. In the PSA and VSA system of prior art, the higher flow rate of breathing fast the patient and/or surpassing 5LPM shows that the oxygen concentration of separating device reduces, typically, when surpassing 6.5LPM, the litre flowmeter that leaves this prior art systems reveals the reducing of 4-8% of the oxygen concentration that generates, the present invention realizes the litre flow of 8-12LPM and does not substantially have or do not have the oxygen concentration impact, less than reducing of 1-2%.
Described alternately orientation specifically be designed for the free radical intermediate that prevents in the oxygen generative process gather (it causes that oxygenous filter decomposes) and excessive water accumulates on the filtering material. Equally, the unexistent design that is used in combination that build-up of electrostatic charges is taken out and discharges the surface filter component that is not adsorbed of prior art can not realize portability certainly.
First screen of filtering material alternately is a kind of porous boron doping type carbon film, at least a anion that it comprises two rutheniums/two ruthenium molecules and is directly connected in carbon film. Second screen that is arranged in the first screen back is made by the synthetic film that comprises at least a zeolite crystal that directly contacts with the CNT of arranged concentric, and described CNT is connected in described synthetic film. Described synthetic film comprises that many diameters are the hole of the about 3.0nm of about 0.1nm-. The crystallization of zeolites body is connected in CNT and covers the hole of at least a portion. But be exactly this structure consist of single repetitive and can arranged in series in order to generate the oxygen of higher yield from given source.
Described synthetic film comprises that many diameters are the hole of the about 3.0nm of about 0.1nm-. The crystallization of zeolites body is connected in CNT and covers the hole of at least a portion. But exactly this structure has consisted of single repetitive and can arranged in series, so that from water vapour, generate many oxygen from water vapour or the another kind of source of exhalation air.
Be used for two rutheniums of the uniqueness of first screen/two ruthenium molecules and comprise several ruthenium atoms. Chemically, " ruthenium " is found with other platinum metals in the ore of the Urals and South and North America usually. But little commercially important amount is also being extracted from Sudbury, the pentlandite of Ontario and finding in the pyroxenite deposit in South Africa. Commercial, separate ruthenium by the chemical method of complexity, wherein use hydrogen that ammonium chloride ruthenium (ammonium ruthenium chloride) was also obtained powder originally. Make the powder associating by PM technique then. In history, ruthenium is to obtain in the residue that stays after with the dissolving of crude product platinum. Ruthenium is a kind of transition metal, and the same with most of transition metal is excellent lewis acid. They accept electronics from the many molecules or the ion that play the lewis base effect easily. When lewis base offers lewis acid with its duplet, describe it as with the lewis acid coordination and form co-ordinate covalent bond. When lewis base also forms whole structural units with the metal-complexing that plays the lewis acid effect, then form complex. In this compounds or compound, lewis base is called as part, and this part can be cationic, anion or electroneutral.
Another part of ruthenium compound of the present invention is multi-metal oxygen acid group or " POM ". As a kind, POM is fully effective as catalyst, and can activate molecular oxygen and/or hydrogen peroxide as the reagent in the oxidation reaction. Yet it is dangerous to use the molecule that comprises ruthenium to poison as one of catalyst main the problem degeneration that is ruthenium catalyst and the people's who contacts ruthenium ion ruthenium, and described ruthenium ion may be expelled out from its combining form/decomposed. The design of filtering material of the present invention partly overcomes these problems by the siderophore that uses unique design.
Charged plates on first screen of filtering material of the present invention comprises boron doped synthetic carbon film and is combined in the synthetic carbon film side relative with the ruthenium compound. The two plays the effect of siderophore synergistically the synthetic carbon film of boron doping and charged plates. Siderophore is the compound of attraction and the free charged ion of combination. In other words, compound can be caught free charged ion before ion continues to come out by filtering material and from filter and enters into people's air-flow. Siderophore of the present invention is electronegative, in order to be specific for the ion of the positively charged that comprises ruthenium ion. Therefore, may be caught from the ruthenium ion of two rutheniums of the present invention/any positively charged that two ruthenium compounds expel out the shortcoming that has overcome the catalyst that uses the ruthenium conduct to be used for generation oxygen the protection that prevents that ruthenium is poisoned also will be provided thus.
One embodiment of the invention are provided for removing from the source filtering material of oxygen and/or hydrogen, comprise having two rutheniums/the porous boron doping type carbon film of two ruthenium molecules and at least a electronegativity ion, described electronegativity ion is directly connected in carbon film, perhaps randomly is connected in carbon film by intermediate compound and/or structure. No matter two rutheniums of the present invention/two ruthenium molecules are directly to contact porous boron doping type carbon film or pass through intermediate compound and/or the structure connection, and they all are ions binding.
In one embodiment of the invention, two ruthenium molecules in each two ruthenium of the present invention/two ruthenium molecules are following formula (I): [Ru2(CO)
4(u-n
2-O
2CR)
2L
2]
x, wherein u is selected from following bridging ligand: [Ru2(EDTA)
2]
2-、(CO)
4、F
-、Co
3 -2、NO
+Aromatic series/the carboxylic acid of (cationic), hydrogen bonding-(be used for multiple connection such as polymerization or single, at oxygen or the interior location of two bondings), ethylenediamine, the halogen ion as the anionic part, carboxylic acid, unsaturated hydrocarbons, linear or crooked and the nitric acid metal center coordination, butadiene, carboxylate part, anionic (RO-And RCO2 -2(wherein R is H or alkyl) or neutral ligand (R2、R
2S、CO、CN
-)、CH
3CN (acetonitrile), NH3(ammonia ammino-complex) F-、Cl
-, three (pyrazolyl) borate (scorpion is closed part, Scorpionate Ligand, a boron is combined with three pyrazoles, this compound-chela (pincers)-referring to can be in conjunction with two pyrazole group (C of metal3H
4N
2) nitrogen heteroatom)) and composition thereof, preferred [Ru2(EDTA)
2]
2-；
Wherein the n minimum is 2, and depends on the number of teeth (denticity) (that is, the number of the donor groups that is connected in the identical central atom of given part) of molecule;
Wherein L is selected from following part: [Ru
2(Ph
2PCH
2CH
2PPh
2) (EDTA)]
2+, C
6H
6, R
2C=CR
2(wherein R is H or alkyl), 1, the two diphenyl phosphine methane of 1-, diethylenetriamine [diene] key (preferred three teeth), 7-triazacyclononane [diene] key (preferred three teeth), triphenyl phosphine and composition thereof;
Wherein CR is carboxylic acid, carboxylicesters part, anionic (RO
-And RCO
2 -(wherein R is an alkyl)) or neutral ligand (R
2, R
2S, CO
-, CN
-(wherein R is an alkyl)) and composition thereof; About 30 for about 1-with x, preferably 1-is about 20, and more preferably 1-about 10.
Another molecule in each two ruthenium of the present invention/two ruthenium molecules is the polyoxometallate of two ruthenium-replacements, for substituting WZnRu with following formula (II)
III 2(OH) (H
2O) (ZnW
9O
34)
2]
-14Na
14[Ru
2Zn
2(H
2O)
2(ZnW
9O
34)
2].Distance between each ruthenium in the two ruthenium molecules is that about 2.0 dusts arrive about 3.18 dusts, and preferred about 2.25 dusts are to about 3.0 dusts, and more preferably from about 2.50 dusts are to about 2.80 dusts.
For example, as at United States Patent (USP) 7,208, disclosed eelctro-catalyst POM in 244 substitutes WZnRu
III 2(OH) (H
2O) (ZnW
9O
34)
2]
-14Na
14[Ru
2Zn
2(H
2O)
2(ZnW
9O
34)
2] the amount of the Ru-Ru distance limit of the 3.18 dusts oxygen that can generate.In addition, because the POM structure of Shi Yonging is reversed when water molecules influences and rotated being subjected in the prior art, so flow in the system of (even in suitable speed time) relating to water water, the continuity that oxygen generates must be restricted.Therefore, two ruthenium POM and two ruthenium sawhorse molecules all were not used to generate respirable oxygen in the past.
In a specific embodiment of the present invention, at the United States Patent (USP) 7 that is merged in this paper people such as Shannon as a reference, 208, the polyoxometallate that two rutheniums described in 244 replace can be used for combining with aforesaid boron doped carbon film, so that the interests of filtering material of the present invention are provided.
In yet another embodiment of the present invention, filtering material comprises the siderophore plate of catching ruthenium ion in addition, and it is connected in the apparent surface of the carbon film that wherein connects two rutheniums/two ruthenium molecules.Described siderophore plate is an ion live-wire, so that catch by the free ruthenium ion of evicting from from described porous boron doping type carbon film.Described siderophore plate can be selected from the ion of electronegative or positively charged, is the resin clay with the hollow tube sheet in a plurality of holes with clay moulding wherein particularly.Especially, siderophore can be the poly--sulfinate resin of dipping, comprise ethylenediamine tetraacetic acid (EDTA) (EDTA) and composition thereof.In a specific embodiment of the present invention, the siderophore plate that the siderophore plate is connected in the end of nanotube of adulterated carbon film and at least a portion is directly connected in film and/or is embedded in the film.This design allows the siderophore plate can catch and ionic bond free ruthenium ion.
Just as discussed above, this to contain the oxygen that filtering material production of ruthenium atom is used to breathe for use be necessary.Be not to be used for breathing but to be used for the embodiment of commercial run by the oxygen of filtering material production therein, the siderophore plate is just so unimportant.
In yet another embodiment of the present invention, porous boron doping type carbon film can comprise the CNT (carbon nano-tube) mesh network in addition.The diameter of the nanotube of CNT (carbon nano-tube) mesh network is that about 20 nanometers arrive about 450 nanometers, and preferred 20 nanometers are to about 250 nanometers, and more preferably from about 20 nanometers are to about 100 nanometers.Described CNT (carbon nano-tube) mesh network is designed to make that each pipe can be with the low relatively big electric current of resistance carrying, and described electric current is used for making oxygen-hydrogen bond instabilityization of water, so that make their easier splitting, in order to produce bimolecular oxygen and/or hydrogen.Correspondingly, energy that the described key that splits is required and time still less make faster thus and more easily produce bimolecular oxygen.The nanotube reticulated structure extends to carrying and arrives about 5.0 microns with POM matrix top about 0.2.
Make two rutheniums be connected in the carbon film from carbon is connected in substrate.In one embodiment of the invention, use silicon substrate or similar substrate permission carbon atom nucleation on substrate surface, cause the reticulated structure of the Sp3 track of tetrahedral coordination from chemical vapor deposition (CDV).CDV is a kind of " heated method ", uses hydrogen and methane as precursor gases.Described heated method for example, can use filament so that the diffusion of active substance (most of is " methyl groups ") to be provided, to be absorbed by the surface with substrate surface interaction and permission carbon atom and to take place to grow coalescent.After finishing, think that the surface of film mainly is to have the single bonded tertiary carbon atom of C-H.
The doping of carbon film can use boron, fluorine and/or nitrogen to carry out.Along with the concentration of doped level improves, the isolator performance change of diamond (carbon) is a kind of in the semi-conductor, and further changes into metallicity completely.In order to realize this electrochemical action, boron doped level must be enough to cause low ohmic voltage drop in diamond (carbon) level, to such an extent as to still can not too lowly change in the doping building-up process or the interference crystalline structure, induces the graphite phase.A kind of method that can realize this purpose is to mix as mixed vapour with fluorine, and wherein when contacting with the carbon film, the two all interacts fluorine and hydrogen and boron, forms key as ion.Another the possible method that realizes this purpose is that the mixture with boron and fluorine comes doping carbon.Using fluorine is a kind of negative adulterated situation, that is, negative F atom has extra electronics and lower slightly energy level (promptly about .028-0.32eV, opposite with about 0.35eV of boron).Typically, carbon-fluorion combination is covalency and very stable, as visible in the several frequently seen fluorocarbon polymer, such as poly-(tetrafluoroethylene) and Teflon.In possibility, the present invention can utilize graphite is deposited on the substrate, so that produce nanotube by the micromechanics separation (micromechanical cleavage) of high quality graphite.
Another alternative embodiment is hydrofluoride (Hydroflourine) vaporization with boron oxide and low volume-mole (be lower than about 0.22 be raised to about 0.34 liter/about 1.9 be raised to about 2.5 liters of methane).Just as discussed above, fluorochemicals such as perfluoroalkyl-organoalkoxysilane and/or trifluoro propyl-Trimethoxy silane (TFPTMOS) can be used for interacting with boron doped carbon film, and prerequisite is that the fluorochemicals per molecule has at least one carbon-to-metal bond.-CF
3With-OCF
3Part provides other variant, more nearest use-SF
5Group.Using another alternative plan of fluorine atom in boron mixes is BF
3
Another alternative plan is that boron oxide and hydrofluoride (Hydrofluroine) gas are vaporized to interact with methane, and use the above-mentioned fluorochemicals of pointing out, such as perfluoroalkyl-organoalkoxysilane, preferably use trifluoro propyl-Trimethoxy silane (TFPTMOS).Essential requirement is that the fluorochemicals per molecule has at least one carbon-to-metal bond).
Now, film plays semi-conductive effect, because in this case, by boron doped rhinestone (carbon) film form shell (its also as anchor), and this combination is used to keep the ruthenium mixture to orientate sawhorse orientation and the maintenance POM over-separation when flow flows through filtering material of the present invention greater than 20 liters/min and/or greater than 4 liters/25 seconds water as.Therefore, boron doped carbon film not only provides semiconductor property, but also plays the effect that prevents that two ruthenium molecules are out of shape under high flow capacity.Boron doped in addition carbon film causes inductive effect with fluorine, and described inductive effect strengthens the electronegativity part and combines with the ruthenium mixture of sawhorse orientation and the part of two inside, and similarly protruding two rutheniums-POM is as the combination of outside simultaneously.
Carbon in diamond or the graphite-structure is Sp
3Hydridization, and boron (non-carbon, i.e. non-diamond) is sp
2.The specific hybridization state of the carbon of above-mentioned discussion and boron is important for electric conductivity is provided for film, makes film not only as the grappling substrate but also as oxygenous electrode.In order to be effective to above-mentioned purpose, film must be about 6 with about 2100ppm-, and 800ppm/0.1cm film (screen) size is carried out boron and mixed.
In yet another embodiment of the present invention, filtering material of the present invention comprises synthetic film in addition, and described synthetic film comprises a plurality of CNT (carbon nano-tube) that connect or embed, to form the CNT (carbon nano-tube) mesh network.Synthetic film of the present invention is selected from SiO
4, AlO
4, and composition thereof.Crystalline structure is based on the repeating unit of the Siliciumatom (+4 valency) that is surrounded by four Sauerstoffatoms (divalent) of tetrahedral configuration.Known tetrahedral clean valency is zero, two shared oxygen molecules of Si atom.When aluminium (+3 valency) was displaced in the tetrahedron orientation, therefore the net charge of generation-1 also caused the cation exchange properties (as discussed further below) of zeolite.The porous boron doping type carbon film surface close communication of siderophore is orientated and be connected with to synthetic film as.Synthetic film of the present invention comprises in addition with synthetic symphysis and connects and/or be embedded at least a zeolite crystal that the CNT (carbon nano-tube) mesh network on the synthetic film directly contacts.Described synthetic film has the many holes of diameter for the about 3.0nm of about 0.1-, and preferred diameter arrives about 3.4nm for about 0.1nm, and more preferably about 2.0nm is to about 2.9nm.
In one embodiment of the invention, the crystallization of zeolites body is directly connected in the CNT (carbon nano-tube) of CNT (carbon nano-tube) mesh network, makes the crystallization of zeolites body cover at least a portion hole in the synthetic film.This structure allows from the oxygen that reaction generated of water molecules and zeolite/nanotube and/or flow hydrogen gas by closing film forming hole, so that collection and be used for given purpose.By the porous boron doping type carbon film that comprises two rutheniums/two rutheniums with comprise the film forming repeating unit that is combined to form filtering material of the present invention of closing of crystallization of zeolites body, described crystallization of zeolites body is connected in the CNT (carbon nano-tube) mesh network, covers at least a portion hole in the synthetic film.
Being used for zeolite of the present invention has by TO
4The crystalline structure of tetrahedral configuration structure, wherein T is Si or Al.Except many naturally occurring zeolites, also has multiple synthetic zeolite.The crystalline structure of zeolite is based on the repeating unit that comprises the Siliciumatom (+4 valency) that is surrounded by four Sauerstoffatoms (divalent) of tetrahedral configuration.Each Sauerstoffatom is shared by two Si atoms, makes that zeolite is that tetrahedral structure and net charge are zero.When being displaced in the tetrahedral configuration, zeolite has-1 net charge at aluminium (+3 valency).This negative charge produces the cation exchange properties of zeolite.Zeolite also has the aperture of qualification very uniformly and high porousness, is because the crystalline structure of their uniqueness.Therefore, zeolite can be used as molecular sieve.
Yet splitted water does not often block the hole of some zeolite, and therefore, these zeolites are often silted up and lose its separating property.The structure of filtering material of the present invention allows zeolite to be connected in the piped mesh network, to keep " not silted up " and effect arranged for a long time, because the nanotube of filtering material makes the hydrogen/oxygen key instabilityization in the water, be oxygen and hydrogen with water splitting thereby make two ruthenium molecules of filtering material easier.Two ruthenium molecule splitted water are many more, and then oxygen/hydrogen generates many more and is used to silt up few more with the water in hole of closing the zeolite that film forming nanotube is connected of the present invention.In case generated oxygen and/or hydrogen, it can be hunted down and be used for breathing, storage or industrial application.
The pore size of the zeolite that uses also is crucial.If Kong Taida, then water can not be split into oxygen and hydrogen by the zeolite filtration device, if Kong Taixiao, then oxygen of Chan Shenging and/or hydrogen can be retained and not by strainer so that be utilized.Therefore, importantly, the hole size of possible minute adjustment zeolite adsorbs specific molecule and gets rid of other molecule based on size so that allow.A method that changes the pore size of zeolite is that tradable positively charged ion is changed into another kind from a kind of positively charged ion.For example, when the Na+ ion in zeolite A was replaced by the Ca++ ion, the effective pore radius increased.This also can realize by changing this Al/Si ratio of zeolite.The increase of the ratio of Si and Al can slightly reduce unit cell dimension, reduces tradable positively charged ion number, therefore makes the passage free time and makes zeolite have more hydrophobicity in nature.
Be used for zeolite of the present invention and mainly be made up of aluminosilicate, wherein alumina substrate comprises alumina pore, and but it plays the effect that allows some atoms get rid of the molecular sieve of other atom, so that the selected final product of purifying.For the application's purpose, term " molecular sieve " is meant the special properties of these materials, that is, and mainly based on the size exclusion method ability of sorting molecule optionally.Can be used for zeolite of the present invention comprises and any (aluminosilicate of basic metal and alkaline-earth metal, described molecule is surrounded by the positively charged ion of sodium, potassium, calcium, strontium or barium) typically in the hydrous alumino silicates mineral substance family perhaps comprises corresponding synthetic compound
Therefore, filtering material of the present invention is made up by the repeating unit that comprises the adulterated film of boron carbon and obtains, described film comprises two ruthenium molecules on a side, and on opposite side, comprise in order to catch the siderophore of free ruthenium ion, be synthetic film and the crystallization of zeolites body that comprises the carbon nano-tube network mesh network subsequently, described carbon nano-tube network mesh network is connected in synthetic film.In these repeating units some assemblings of can connecting are so that be provided for the filtering material that high output oxygen and/or hydrogen generate.The filtering material of this uniqueness has made up two kinds of different materials, produces the novel material with the feature that is different from basic material.Thereby filtering material of the present invention not only electrolysis generates a large amount of bimolecular oxygen but also utilizes and directly pass through to filter, and catches bimolecular oxygen by molecular sieve " zeolite media " and is used for respiration apparatus, storage or industrial application.
Be embedded in the synthetic lip-deep CNT (carbon nano-tube) mesh network of film and extend to the synthetic film surface about 0.1 of zeolite coating to about 7 millimeters, preferred about 0.2 to about 6 millimeters, more preferably from about 0.2 to about 6 millimeters.As the nanotube relevant with the adulterated film of the carbon that comprises two rutheniums, described CNT (carbon nano-tube) can have the diameter of about 20 nanometers to about 450 nanometers.Any that can use following method is embedded in the CNT (carbon nano-tube) mesh network on the synthetic film surface, charged molecule China ink, the crystallization self-assembly (crystallizationself-assembly) of E-beam lithography, atomic force microscopy, chemistry, introduce crystal seed self-assembly (seeded self-assembly), with and combination, and do not influence any other method of closing film forming hole that it is embedded.
Can use an application of the present invention is that employing is directly visual in telescopiny, as " IBM Almaden ' s Materials Characterization and Analysis Lab ", it uses FEI 830Dual Beam system, with FIB (focused ion beam, Focused Ion Beam) integrated with ultrahigh resolution SEM, allow the analyst mill or deposition process in catch the image of specific position.When preparation carbon film, at first mill film so that dig out initial hole by the gallium ion that quickens, be used to CNT (carbon nano-tube) to embed boron doped film.After finishing, the carbon metal oxide is deposited in the zone of milling, to form the downside of pattern and carbon pipe, will be pumped on the surface of film such as the rare gas element of argon gas simultaneously.With the adulterated atomic deposition of other carbon on the argon gas surface above the CNT (carbon nano-tube) recess that forms in film by gallium ion in advance.Deposition can be undertaken by ALD (ald) or CVD, makes the carbon pipe present the outwardly directed concentric pattern of inner most point from film.After forming carbon nanotube, the terminal portions maintenance of carbon nanotube is open, so that apply electric current in the inside of carbon nanotube.Then two ruthenium molecules are atomised on the surface of preparation or use CVD to apply, so that combine with the boron fluorine at freshly prepd film surface.
In alternative plan, the method that is used to form the boron doped fluoride film of carbon can be at Ar-FI
2Use in the gaseous mixture and comprise that the mixture target of h-BN and graphite carries out rf magnetron sputtering, described Ar-FI
2Gaseous mixture forms to form argon gas bifluoride (HArF) by photodissociation hydrogen fluoride in solid argon gas matrix.After forming, can learn by X-ray diffraction, Fourier transform infrared spectroscopy and/or x-ray photoelectron spectroscopy and characterize the adulterated fluorion film of carbon.The description of these methods can
Preparation of boron carbon nitride thin Films by radio frequency magnetron sputtering.Applied Surface Science, Volume 252, and Issue 12, and 15April 2006, Pages 4185-4189..Lihua Liu, YuxinWang, Kecheng Feng, Yingai Li, Weiqing Li, Chunhong Zhao, YongnianZhao; With
A stable argon compound.Leonid Khriachtchev, MikaPettersson, Nino Runeberg, Jan Lundell﹠amp; Markku Rasanen.Departmentof Chemistry, PO Box 55 (A.I.Virtasen aukio 1), FIN-00014University ofHelsinki, Finland.Nature 406, and 874-876 finds in (24August 2000).
The two CNT (carbon nano-tube) mesh network of boron doped film and synthetic film can begin outwards to be arranged as the circle that concentric spacing is opened from the central zone of porous boron doping type carbon film or zeolite synthesis film.
Generally speaking, filtering material of the present invention is designed to make that zeolite synthesis film screen is positioned at the back of the boron doped film screen of two rutheniums, makes two rutheniums shield the nearside at air-flow, that is, air-flow at first contacts two rutheniums screen.Like this, being included in moisture in the air-flow is affected and obtains promoting on electrochemistry opening and being hydrogen and oxygen to strengthen water crack.Zeolite and two rutheniums screen pull together to work.In a preferred embodiment of the invention, can be used in the cartridge filter that the patient respiratory device uses, comprising the hexad screen with framework.Can be after producing by FTIR and/or X-ray crystalline diffraction method to two ruthenium centers with accompany and combine with two ruthenium walls and analyze its tolerance range and bonded contact surface by the external margin at the zeolite center of two ruthenium walls encirclement.
Cartridge filter is designed to make it to take off where necessary and to change.Cartridge filter can be produced to can recirculation maybe being the device that single uses.Cartridge filter may have many different structures, does not limit or changes the functional of filtering material of the present invention.That is to say, alternative filtering material between the boron doped film of two novel rutheniums/two rutheniums screen and novel zeolite synthesis film screen is provided, described boron doped film screen and zeolite synthesis film screen pull together to work, and are used for the individual patient breathing, are used for the oxygen storing unit or are used for industrial user's bimolecular oxygen so that produce.Unique design of the present invention prevents the accumulation of free radical intermediate in the oxygen generative process simultaneously and prevents to be used for the oxygen catalyst of filtering material of the present invention and the decomposition of anion electrode.
Specific embodiments of the present invention is described with reference to the drawings, provides described embodiment to be used for describing the present invention better and should not regard as and limit the present invention by any way.
Fig. 1 shows the front prediction view of the porous boron doping type carbon film that comprises two rutheniums/two ruthenium molecules of filtering material of the present invention (10).With shown in Fig. 1, the Web materials of screen is the boron doped screen of carbon (15) as mentioned above, has top margin (55), base (60), the right (45) and the left side (50).Such as alternative shape of circle, oval-shaped, ovate, parallelogram also within the scope of the invention, particularly square, rectangle and trilateral.
Fig. 1 shows the orthogonal screen that only is used to describe purpose, but other shape also is considered within the scope of the present invention.Being provided with or being embedded in the boron doped screen of carbon (15) is CNT (carbon nano-tube) (20), the loop construction that its central point from screen begins and outwards radiation forms the loose assembling of arranged concentric.Although CNT (carbon nano-tube) is an arranged concentric, in alternative plan, depend on the design and the shape of the boron doped screen of carbon (15), can be with different patterned arrangement CNT (carbon nano-tube).The difference of nanotube is arranged, and is the same with the different shapes of screen, also is considered within the scope of the present invention.
Being applied in the middle dispersive of the boron doped screen of carbon (15) is many boron atoms (25).These boron atoms (25) can run through whole screen and disperse equably, perhaps can concentrate on the CNT (carbon nano-tube) intra-zone.About region intermediate of nano-sized carbon screen (15) is multi-metal oxygen acid group (POM) mixture (40) that at least one two ruthenium replaces.As mentioned above, in one embodiment of the invention, two rutheniums replace multi-metal oxygen acid group (POM) mixture (40) and comprise the two ruthenium sawhorse molecules (35) that are connected in POM (30).Two ruthenium sawhorse molecule (35) positions are contiguous with screen, and the surface that POM (30) stretches out screen.This arrangement allows water to be degraded to bimolecular oxygen and hydrogen fast and efficiently.This arrangement constitutes first screen of the repeating unit of filtering material of the present invention.
Fig. 2 shows the back side prediction view of the porous boron doping type carbon film (100) that comprises two rutheniums/two ruthenium molecules and siderophore (115).The boron doped screen of carbon of the present invention has top margin (105), base (110), the left side (120) and the right (125).Siderophore shown in Fig. 2 (115) is positioned at the base (110) of screen, and still, the other parts that siderophore (115) is positioned at screen are intended to the scope of the invention, depend on the shape of screen and the arrangement of nanotube.Multi-metal oxygen acid group (POM) mixture (40) that the boron doped screen of carbon (15) comprises localized as shown in fig. 1 boron atom (25) and carbon nanotube (20) and replaces with at least one two ruthenium of above-mentioned discussion as shown in Figure 1.
Siderophore (115) can be the form with the tubular structure in a plurality of holes, and wherein at least one of siderophore (115) is terminal directly is communicated with at least one end of CNT (carbon nano-tube).In alternative plan, siderophore (115) can be the form of ion band electroplax.Arbitrary structure all is to be designed for to catch charged ion, such as the ruthenium ion that may be evicted from from filtering material, avoids breathing the free ruthenium ion so that the patient of the oxygen that is produced by described filtering material is breathed in protection.Plate or hollow tube siderophore (115) can be made up by the poly--sulfinate resin of dipping, ethylenediamine tetraacetic acid (EDTA) (EDTA) and composition thereof and obtain.
Fig. 3 shows the sectional view on surface of the synthetic film (200) that comprises the crystallization of zeolites body of filtering material of the present invention.This is the next one screen in the strainer repeating unit, and orientates as towards the rear surface of the boron doping type carbon film with siderophore shown in Fig. 2.Synthetic film (200) has top margin (205), base (210), the right (220) and the left side (225), and is depicted as the orthogonal profile.The same with the situation of single screen, synthetic screen is depicted as the orthogonal shape, but has considered such as alternative shape of circle, ellipse, oval, parallelogram also within the scope of the invention, particularly square, rectangle and leg-of-mutton.That is to say that Fig. 3 shows the orthogonal screen that only is used to describe purpose, but other shape also within the scope of the present invention.
The same with the boron doping type carbon film among Fig. 1 and Fig. 2, synthetic film has and embeds or disposed thereon carbon nanotube.Synthetic screen also has and nanotube (215), synthetic film or its two crystallization of zeolites body (240) that directly contacts.
Fig. 4 shows a plurality of alternately sectional views of screen (300) of filtering material of the present invention.Alternately stacked arrangement comprises the first boron doping type carbon film, and it comprises two rutheniums/two ruthenium molecules and at least one siderophore (305).In the filtering material of the present invention second screen is the synthetic film (310) that comprises zeolite, and its back is another boron doped carbon screen (315), is another synthetic film (320) that comprises zeolite then.The screen of this two types repeat to replace stacked can the repetition, up to the screen number that obtains expecting.This screen can have framework separately, is enclosed in the cartridge filter, and perhaps in alternative plan, screen can be frameless and be enclosed in the cartridge filter with frameless form.Cartridge filter has guaranteed to be repeated to shield by alternative the integrity of the filtering material of manufacturing.
Fig. 5 shows a plurality of alternately prediction views of screen of the filtering material of the present invention in cartridge filter (400).This cartridge filter (400) can have many different shapes and size, and can be used on the generation breathing with in the machine of oxygen, perhaps in alternative plan, as mentioned above, is used for the oxygenous device of industrial purposes.
Although above description comprises many details, should not regard these details as limitation of the present invention, and be the illustration of its preferred embodiment.Those skilled in the art can be contemplated to many other embodiments in the defined the scope and spirit of the present invention of claim.
Claims (21)
1. be used for generating from the source/removing the filtering material of oxygen and/or hydrogen, comprise:
Porous boron doping type carbon film, the negatively charged ion that comprises two rutheniums/two ruthenium molecules and at least a type, described two rutheniums/two ruthenium molecules are orientated as with described porous boron doping type carbon film with described negatively charged ion and are directly contacted, thereby generate oxygen and/or hydrogen from described source when crossing described filtering material in described source.
2. the filtering material of claim 1 is ionically bonded with described two rutheniums/two ruthenium molecules that described porous boron doping type carbon film directly contacts wherein.
3. the filtering material of claim 1, wherein said porous boron doping type carbon film comprises the CNT (carbon nano-tube) mesh network in addition.
4. the filtering material of claim 1, wherein one two ruthenium molecule of each described two rutheniums/two ruthenium molecule is represented by following formula (I):
[Ru
2(CO)
4(u-n
2-O
2CR)
2L
2]
x (I)
Wherein u is selected from following bridgingligand: [Ru
2(EDTA)
2]
2-, (CO)
4, F
-, Co
3 -2, NO
+Aromatic series/the carboxylic acid of (cationic), hydrogen bonding-(being used for multiple connection such as polymerization or one), quadrol, halogen ion, carboxylic acid, unsaturated hydrocarbons, linear or crooked and metal center coordinate nitric acid, divinyl, carboxylicesters part, anionic (RO as the anionic part at the oxygen or the interior location of two bondings
-And RCO
2 -2(wherein R is H or alkyl) or neutral ligand (R
2, R
2S, CO, CN
-), CH
3CN (acetonitrile), NH
3(ammonia ammine) F
-, Cl
-, three (pyrazolyl) borate and composition thereof, preferred [Ru
2(EDTA)
2]
2-
Wherein the n minimum is 2, and depends on the number of teeth (that is the number of the donor groups that is connected in the identical central atom of given part) of molecule;
Wherein L is selected from following part: [Ru
2(Ph
2PCH
2CH
2PPh
2) (EDTA)]
2+, C
6H
6, R
2C=CR
2(wherein R is H or alkyl), 1, the two diphenyl phosphine methane of 1-, diethylenetriamine [diene] key (preferred three teeth), 7-triazacyclononane [diene] key (preferred three teeth), triphenyl phosphine and composition thereof;
Wherein CR is carboxylic acid, carboxylicesters part, anionic (RO
-And RCO
2 -(wherein R is an alkyl)) or neutral ligand (R
2, R
2S, CO
-, CN
-(wherein R is an alkyl)) and composition thereof; With
X is about 1-about 30.
5. the filtering material of claim 4, one two ruthenium molecule of two rutheniums of wherein said formula (I)/two ruthenium molecules are connected in the multi-metal oxygen acid group that two rutheniums of following formula (II) replace:
[WZnRu
III 2(OH)(H
2O)(ZnW
9O
34)
2]
-14 (II)。
6. the filtering material of claim 5, the siderophore plate of catching ruthenium ion that comprises the apparent surface who is connected in the described porous boron doping type carbon film that wherein connects described at least one two ruthenium/two ruthenium molecules in addition, ion live-wire during described siderophore plate is so that catch from the dispossessed free ruthenium ion of described porous boron doping type carbon film.
7. the filtering material of claim 6, wherein said siderophore plate are selected from poly--sulfinic acid ester resin-impregnated sheet, ethylenediamine tetraacetic acid (EDTA) (EDTA) and composition thereof.
8. the filtering material of claim 5, the distance between each ruthenium in the wherein said two ruthenium molecules is about 2.75 dusts.
9. the filtering material of claim 8, the diameter of the described nanotube of wherein said CNT (carbon nano-tube) mesh network are that about 20 nanometers are to about 450 nanometers.
10. the filtering material of claim 4, wherein x is 1 to about 10.
11. the filtering material of claim 5, comprise synthetic film in addition, described synthetic film comprises and connects and/or be embedded in described closing on the film forming surface to form a plurality of CNT (carbon nano-tube) of CNT (carbon nano-tube) mesh network that described synthetic film is orientated as and the described surperficial close communication that comprises the described porous boron doping type carbon film of described siderophore.
12. the filtering material of claim 11, comprise at least a zeolite crystal that directly contacts with described CNT (carbon nano-tube) in addition, wherein said synthetic film comprises a plurality of holes of the about 3.0nm of the about 0.1-of diameter, the described crystallization of zeolites that wherein is connected with described CNT (carbon nano-tube) covers the described hole of at least a portion, to form the repeating unit of described filtering material, be used for removing oxygen and/or hydrogen from the source.
13. the filtering material of claim 11, wherein said synthetic film is SiO
4, AlO
4And composition thereof.
14. the filtering material of claim 11 wherein is embedded in and describedly closes film forming described lip-deep described CNT (carbon nano-tube) mesh network and extend about 0.2 millimeter to about 5 millimeters in described surface.
15. the filtering material of claim 12, the diameter of the described CNT (carbon nano-tube) of wherein said CNT (carbon nano-tube) mesh network are that about 20 nanometers are to about 450 nanometers.
16. the filtering material of claim 12 wherein uses E-beam lithography, atomic force microscopy, charged molecule China ink, crystallization self-assembly, the self-assembly of introducing crystal seed and the combination thereof of chemistry that described CNT (carbon nano-tube) mesh network is embedded in described closing on the film forming described surface.
17. the filtering material of claim 2, wherein said CNT (carbon nano-tube) mesh network are arranged as from the central zone of described porous boron doping type carbon film and begin the circle that outside concentric spacing is opened.
18. the filtering material of claim 11 wherein is embedded in the described film forming described lip-deep CNT (carbon nano-tube) of closing of zeolite that comprises and is arranged as from the central zone of described porous boron doping type carbon film and begins the circle that outside concentric spacing is opened.
19. the filtering material of claim 5, the polyoxometallate that described two rutheniums of its Chinese style (II) replace is Na
14[Ru
2Zn
2(H
2O)
2(ZnW
9O
34)
2].
20. the filtering material of claim 12, the polyoxometallate that described two rutheniums of its Chinese style (II) replace is Na
14[Ru
2Zn
2(H
2O)
2(ZnW
9O
34)
2].
21. produce oxygen and/or the method for hydrogen, comprise the aqueous airflow that the filtering material that passes claim 12 is provided, to produce oxygen and/or hydrogen from described filtering material.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US96775607P | 2007-09-07 | 2007-09-07 | |
| US60/967,756 | 2007-09-07 | ||
| PCT/US2008/010388 WO2009035525A2 (en) | 2007-09-07 | 2008-09-05 | A filter material for generating oxygen and/or hydrogen from a source |
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|---|---|
| CN101835707A true CN101835707A (en) | 2010-09-15 |
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ID=40343673
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| Country | Link |
|---|---|
| US (5) | US20090071471A1 (en) |
| EP (3) | EP2188208A2 (en) |
| JP (3) | JP2010537821A (en) |
| KR (3) | KR20100100752A (en) |
| CN (1) | CN101835707A (en) |
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| US8701718B1 (en) | 2006-08-16 | 2014-04-22 | Rescue Air Systems, Inc. | Emergency air system and method of a marine vessel |
| JP2013521114A (en) * | 2010-03-05 | 2013-06-10 | コーニンクレッカ フィリップス エレクトロニクス エヌ ヴィ | Oxygen separation membrane |
| US20120160247A1 (en) * | 2010-12-22 | 2012-06-28 | Quincy Iii Roger B | Splash Resistant Facemask |
| CN102198354A (en) * | 2011-05-10 | 2011-09-28 | 无锡国赢科技有限公司 | Filter structure for purifying hydrogen gas |
| US9102529B2 (en) | 2011-07-25 | 2015-08-11 | H2 Catalyst, Llc | Methods and systems for producing hydrogen |
| JP5993007B2 (en) | 2011-08-15 | 2016-09-14 | エンパイア テクノロジー ディベロップメント エルエルシー | Oxalate sorbent for mercury removal |
| GB201119283D0 (en) | 2011-11-08 | 2011-12-21 | Univ Glasgow | Apparatus and methods for the electrochemical generation of oxygen and/or hydrogen |
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| US9623204B2 (en) | 2012-08-20 | 2017-04-18 | Hydro Healer, Llc | Electrolysis system and apparatus for collecting hydrogen gas |
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| US20210060282A1 (en) * | 2018-01-09 | 2021-03-04 | Takashi TAKEHARA | Portable gas supply device |
| GB201801170D0 (en) | 2018-01-24 | 2018-03-07 | Univ Court Univ Of Glasgow | Use of polyoxometalate mediators |
| CN110125464B (en) * | 2019-05-09 | 2020-06-23 | 哈尔滨工业大学 | Potentiometer linearity synchronous and continuous trimming system and trimming method |
| KR20220144426A (en) | 2021-04-19 | 2022-10-27 | 주식회사 지비비케이 | Hydrogen gas-oxygen gas supply apparatus |
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| US2944627A (en) * | 1958-02-12 | 1960-07-12 | Exxon Research Engineering Co | Method and apparatus for fractionating gaseous mixtures by adsorption |
| US3313091A (en) * | 1963-11-04 | 1967-04-11 | Exxon Research Engineering Co | Vacuum cycle adsorption |
| US4222750A (en) * | 1976-08-16 | 1980-09-16 | Champion Spark Plug Company | Oxygen enrichment system for medical use |
| JP3740295B2 (en) * | 1997-10-30 | 2006-02-01 | キヤノン株式会社 | Carbon nanotube device, manufacturing method thereof, and electron-emitting device |
| DE10051910A1 (en) * | 2000-10-19 | 2002-05-02 | Membrana Mundi Gmbh | Flexible, porous membranes and adsorbents, and processes for their manufacture |
| US7085125B2 (en) * | 2002-03-21 | 2006-08-01 | Chien-Min Sung | Carbon nanotube devices and uses therefor |
| JP4042526B2 (en) * | 2002-10-22 | 2008-02-06 | 株式会社日立製作所 | Sheet electrolyte membrane electrode assembly and fuel cell using the same |
| CN1234604C (en) * | 2002-11-27 | 2006-01-04 | 清华大学 | Carbon nano pipe, its preparation process and equipment |
| US7208244B2 (en) * | 2003-10-15 | 2007-04-24 | Auburn University | Di-ruthenium-substituted polyoxometalate electrocatalyst and method of oxygen generation |
| WO2005049900A1 (en) * | 2003-11-21 | 2005-06-02 | Mitsubishi Heavy Industries, Ltd. | Carbon nano fibrous rod and fibrous nano carbon, and method and apparatus for preparing fibrous nano carbon |
| US7144753B2 (en) * | 2003-11-25 | 2006-12-05 | Board Of Trustees Of Michigan State University | Boron-doped nanocrystalline diamond |
| US7226842B2 (en) * | 2004-02-17 | 2007-06-05 | Intel Corporation | Fabricating strained channel epitaxial source/drain transistors |
| US7381683B1 (en) * | 2004-10-28 | 2008-06-03 | Nanostellar, Inc. | Method of producing multi-component catalysts |
| GB0504445D0 (en) * | 2005-03-03 | 2005-04-06 | Univ Cambridge Tech | Oxygen generation apparatus and method |
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2008
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- 2008-09-05 US US12/231,799 patent/US20090071471A1/en not_active Abandoned
- 2008-09-05 KR KR1020107007599A patent/KR20100100752A/en not_active Application Discontinuation
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| US20090071471A1 (en) | 2009-03-19 |
| WO2009035526A2 (en) | 2009-03-19 |
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| EP2188207A2 (en) | 2010-05-26 |
| EP2188208A2 (en) | 2010-05-26 |
| WO2009035545A2 (en) | 2009-03-19 |
| WO2009035526A9 (en) | 2010-04-22 |
| US20090272273A1 (en) | 2009-11-05 |
| KR20100111659A (en) | 2010-10-15 |
| US20110135563A1 (en) | 2011-06-09 |
| KR20100100752A (en) | 2010-09-15 |
| WO2009035525A2 (en) | 2009-03-19 |
| US20090074654A1 (en) | 2009-03-19 |
| CA2698529A1 (en) | 2009-03-19 |
| CA2698530A1 (en) | 2009-03-19 |
| US7794865B2 (en) | 2010-09-14 |
| JP2010537944A (en) | 2010-12-09 |
| KR20100100753A (en) | 2010-09-15 |
| US20090071472A1 (en) | 2009-03-19 |
| US7579103B2 (en) | 2009-08-25 |
| EP2188209A2 (en) | 2010-05-26 |
| JP2010537819A (en) | 2010-12-09 |
| JP2010537821A (en) | 2010-12-09 |
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